Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals

Definitions

• the present invention relates to a priming system for anionic polymerization of (meth) acrylic monomers and also of ethylenically unsaturated comonomers; this new boot system allows good control of the anionic polymerization of these monomers, in especially at high temperatures.
• anionic polymerization of (meth) acrylic monomers is often complicated by the side reactions of the monomers both with the initiator and with the ends of growing anionic chains, and by the termination and chain transfer reactions.
• this type of polymerization is interesting by the fact that one can obtain polymers having a well-defined structure if it can be carried out under conditions carefully controlled, often requiring very low temperatures polymerization to minimize or eliminate termination reactions and chain transfer.
• poly (methyl methacrylate) comprising a rate of syndiotactic triads higher than that which can be obtained in conventional radical polymerization, at the same temperature (for example, the rate of syndiotactic triads is from about 50% to 60% in radical polymerization).
• R 1 , R 2 and R 4 may each represent, independently, a methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl or phenyl radical and preferably, methyl;
• R 3 and R 5 may each independently represent an ethylene, propylene, butylene or isobutylene radical, and preferably ethylene;
• M preferably represents lithium, and m is preferably equal to zero or 1.
• Amino alcoholates (2) are known compounds, which are prepared, for example, by reaction of a compound (II): with any base whose pKa is greater than the pKa of the alcoholate (I) / alcohol (II) pair.
• lithium aminoalcoholates can be prepared by reaction with an organometallic compound of lithium or metallic lithium in polar or nonpolar solvent.
• the initiator (1) of the initiation system according to the invention can be any monofunctional or difunctional initiator known for anionic polymerization.
• the monofunctional initiator can also be an ⁇ -lithioisobutyrate and amidures.
• Monofunctional initiators are, for example, sec.-butyllithium, n-butyllithium, fluorenyllithium, alphamethylstyryllithium, 1,1-diphenylhexyllithium, diphenylmethyl-lithium or -sodium or -potassium and 1,1-diphenyl-3-methylpentyllithium.
• the difunctional initiator can be chosen in particular from compounds such as 1,1,4,4-tetraphenyl-1,4-dilithio-butane, 1,1,4,4-tetraphenyl-1,4-disodiobutane.
• the molar ratio of the alkali metal amino alcoholate (2) to the initiator (1) in the priming system according to the invention can vary within very limited wide.
• the amount of aminoalcoholate (2) depends on the initiator (1) chosen and on or monomers to be polymerized.
• the aminoalcoholate / initiator molar ratio, according to the invention is between 1 and 200, preferably being between 5 and 100, particularly greater than 10.
• the present invention also relates to a polymerization process anionic of (meth) acrylic monomers and optionally of monomers with ethylenic unsaturation (s) copolymerizable with the monomers (meth) acrylics, characterized in that the polymerization is carried out presence of a priming system as defined above.
• the polymerization temperature can vary between -100 ° C and + 100 ° C, preferably between -10 ° C and + 90 ° C and, more particularly, it is lower or equal to + 70 ° C.
• the polymerization, carried out in the presence of the priming system according to the invention preferably takes place in the absence of moisture and oxygen, and, in presence of at least one non-protic solvent, preferably apolar or mostly apolar.
• the solvent can be chosen, preferably, from benzene, toluene, ethylbenzene, tetrahydrofuran, diglyme, tetraglyme, orthoterphenyl, biphenyl, decalin, tetralin or their mixtures; toluene or ethylbenzene are advantageously used.
• We can also use a toluene-tetrahydrofuran or ethylbenzene-tetrahydrofuran mixture may contain up to 10% by volume of tetrahydrofuran.
• the priming system according to the invention allows total conversion monomers in a period of less, generally much less, than 30 minutes, this duration being dependent on the temperature. In the case of polymerization of acrylates, this duration can be much less than one second.
• the polymerization according to the invention is possible in type reactors batch or tubular, but it is not limited to these.
• the monomer (s) to be polymerized and the priming system are first mixed in a micromixer (by example cyclone or tangential jet micromixer, of the jet type impact), then the mixture is injected into the (co) polymerization reactor.
• a micromixer by example cyclone or tangential jet micromixer, of the jet type impact
• the duration of stay of the monomer (s) and of the initiation system in the micromixer is less than the (co) polymerization time.
• the polymerization can take place under adiabatic conditions. This is interesting since there is no need to supply energy during the polymerization.
• the monomers which can be (co) polymerized by the process of the invention are the (meth) acrylic monomers, and the monomers containing ethylenic unsaturation (s) copolymerizable with these monomers (meth) acrylics. These are chosen in particular from the monomers vinyl aromatics, optionally substituted, for example, with halogens, diene monomers, vinylidene monomers, monomers olefins and vinyl-2 and vinyl-4 pyridine, vinylsilanes, vinylaldehydes, vinyl ketones, vinyl sulfoxides and alkylcyanoacrylates. We can also use heterocyclic monomers.
• (meth) acrylic monomer means a monomer chosen from the (meth) acrylates of the formulas respectively: in which R 0 is chosen from C 1 -C 18 alkyl radicals, linear or branched, primary, secondary or tertiary, C 5 -C 18 cycloalkyl, alkoxy-alkyl and alkylthio-alkyl in which the alkyl group, linear or branched, has from 1 to 8 carbon atoms, aryl and arylalkyl, these radicals being optionally substituted by at least one fluorine atom and / or at least one hydroxyl group after protection of this hydroxyl group; glycidyl, norbornyl, isobornyl (meth) acrylates, mono- and di- (C 1 -C 18 alkyl) - (meth) acrylamides.
• methacrylates examples include methyl, ethyl, 2,2,2-trifluoroethyl, n-propyl methacrylates, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-amyl, i-amyl, n-hexyl, 2-ethylhexyl, cyclohexyl, octyl, i-octyl, nonyl, decyl, lauryl, stearyl, phenyl, benzyl, ⁇ -hydroxy-ethyl, isobornyl, hydroxypropyl, hydroxybutyl.
• the methacrylic monomer preferred is methyl methacrylate.
• acrylates of the above formula mention may be made of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl acrylates, tert.-butyl, hexyl, 2-ethylhexyl, isooctyl, 3,3,5-trimethylhexyl, nonyl, isodecyl, lauryl, octadecyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl.
• vinyl aromatic monomer within the meaning of the present invention, it is means an ethylenically unsaturated aromatic monomer such as styrene, vinyltoluene, alphamethylstyrene, methyl-4-styrene, methyl-3-styrene, methoxy-4-styrene, hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy-4-styrene, dimethyl-3,4-styrene, tert.-butyl-3-styrene and vinyl-1-naphthalene.
• aromatic monomer such as styrene, vinyltoluene, alphamethylstyrene, methyl-4-styrene, methyl-3-styrene, methoxy-4-styrene, hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy-4-styrene
• diene monomer is meant a diene chosen from dienes linear or cyclic, conjugated or non-conjugated as for example the butadiene, 2,3-dimethyl-butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadienes, 5-ethylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene.
• olefinic monomers mention may be made of ethylene.
• the aminoalcoholates used are lithium 2- [N- (2-dimethylaminoethyl) -N-methylamino] ethylate (Ia): and lithium 2- (dimethylamino) ethylate (Ib):
• MMA methyl methacrylate
• Toluene and THF were fractionated and then refluxed on potassium and introduced into a round bottom flask connected to a pipe under empty. After degassing, the mixture was stirred with 5 ppm benzophenone on a sodium / potassium alloy (1/3) until the solution turns blue, then it was distilled again just before use.
• the initiator is obtained by reaction of an equivalent of n-butyllithium (1.3 M in solution in a cyclohexane / hexane mixture) with an equivalent of DPE, in THF at -40 ° C (or in toluene at + 30 ° C).
• the aminoalcoholates are prepared in situ by reaction of the alcohols (distilled on magnesium and stored under nitrogen) or with initiator.
• Steric exclusion chromatography is done on a device Varian equipped with dual UV / RI detection and TSK type columns calibrated with polystyrene standards. THF is used as an eluent.
• the tacticity of the polymers is determined by 1 H NMR, carried out on a Brucker AC200 device (200 MHZ).
• Example 1 The procedure is as in Example 1, by modifying the operating conditions as shown in Table 1.
• the present invention allows, for the first time, controlled anionic polymerization of methyl methacrylate at temperatures as high as 70 ° C., in non-polar medium, in the presence of a ligand of a new associated type to a classic initiator.

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Citations (6)

• 1997
  • 1997-04-10 FR FR9704469A patent/FR2761996B1/fr not_active Expired - Fee Related
• 1998
  • 1998-03-31 EP EP98400749A patent/EP0870776A3/de not_active Withdrawn
  • 1998-04-07 CA CA002232454A patent/CA2232454A1/fr not_active Abandoned
  • 1998-04-10 US US09/058,503 patent/US20010003726A1/en not_active Abandoned
  • 1998-04-10 JP JP10099698A patent/JP2862868B2/ja not_active Expired - Lifetime

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